CN101384656A

CN101384656A - Aromatic sulphonate flame retardant compositions

Info

Publication number: CN101384656A
Application number: CNA2007800052682A
Authority: CN
Inventors: C·布赖纳; T·埃利斯; R·霍克伯格; S·尼塞尔
Original assignee: Ciba SC Holding AG
Current assignee: BASF Schweiz AG
Priority date: 2006-02-14
Filing date: 2007-02-05
Publication date: 2009-03-11

Abstract

The invention relates to flame retardant compositions, wherein salts of selected aromatic sulphonic acids are present in a polycarbonate substrate. The compositions attain the desirable V-0 rating, according to UL-94 (Underwriter's Laboratories Subject 94) and other excellent ratings in related test methods while preserving the excellent mechanical, chemical and thermal properties of polycarbonates, such as light transparency.

Description

Aromatic sulphonate flame retardant compositions

The present invention relates to comprise the fire-retardant combination of the salt of selected aromatic sulfonic acid and polycarbonate and relate to the method that flame retardant resistance is provided to the polymeric substrate of the salt that comprises polycarbonate and selected aromatic sulfonic acid.

Polycarbonate be have high tenacity, outstanding transparency, with the good consistency of multiple polymers and the thermoplastic polymer of high thermal deformation resistant.Polycarbonate is corresponding to general formula:

At commercial topmost polycarbonate is 2, and 2-two (4-hydroxyphenyl) propane polycarbonate (1) is also referred to as bisphenol-a polycarbonate [24936-68-3] (BPA-PC):

Referring to Ullmann ' s Encyclopaedia of Industrial Chemistry, On-LineEdition, Wiley-VCH, DOI:10.1002/14356007.a21_207 and enter Polycarbonate, Roempp On-line, www.roempp.com.

The various additives that are used to improve machinery, chemistry and the thermal properties of polycarbonate are known.The end capped polycarbonate of fluorocarbon can be used for various technology and uses, as be used for the surface energy depressant (reducers of surface energy) of organic materials, " surface-modifying agent " is preferably polycarbonate, polyester, polyacrylic ester or polymethacrylate or their mixture, blend or alloy.Polymkeric substance with surface energy of this reduction has desirable character, as " easy to clean ", " automatically cleaning ", " anti-soil ", " decontamination stain ", " anti-scribble ", " oil resistant ", " anti-solvent ", " chemicals-resistant ", " self-lubricating ", " scratch resistance ", " low moisture absorption " and " hydrophobic " surface.The preparation of the end capped polycarbonate of useful especially fluorocarbon is described among the international patent application No.PCT/EP2004/053331.

In polymer materials (synthetic or natural), add fire retardant to strengthen the flame-retardant nature of this polymkeric substance.According to their composition, fire retardant can work with chemical mode (for example, by emitting nitrogen as pore forming material) and/or with physics mode (for example by producing foam deck) in solid phase, liquid phase or gas phase.During the specified phase of combustion processes (for example during heating), fire retardant disturbs and decomposes, lights or propagation of flame.

It is known adding fire retardant in polycarbonate, referring to J.Troitzsch, and PlasticsFlammability Handbook, the 3rd edition, Hanser Publishers, Munich2004, pp.158-172 (ISBN3-446-21308-2).

Is specially suitable based on the fire retardant of basic metal, alkaline-earth metal or ammonium salt when the lower concentration.In these salt, it is more a kind of that perfluoroalkane sulfonates belongs to.They are used as fire retardant in polycarbonate be known; Referring to people such as T.Ishikawa, Journal of MacromolecularScience, Part A-Pure and Applied Chemistry, Vo1.A41, No.5, pp.523-535,2004.

Requiring thickness of sample to be less than or equal in 1.6 millimeters the application, the flame retardant resistance of V-0, according to UL-94 (Underwriter ' s Laboratories Subject 94), obtain by adding so-called anti-dripping agent (anti-dripping agent) (as tetrafluoroethylene).The fire retardant that has proposed other is additive altogether, as phosphoric acid halogenated aryl ester (haloarylphosphates), and referring to US Patent specification No.5,478,874 or guanidinesalt, referring to US Patent specification No.6,518,340.In various reference, proposed to add the polysiloxane of different structure; Referring to US Patent specification No.6,660,787,6,727,302 or 6,730,720.The problem of finding these additives is: the concentration of fire retardant must be enhanced to reach the V-0 grade, and this machinery to polycarbonate, chemistry and thermal properties are harmful.

Therefore, the present invention relates to find suitable additive, it can be applied in the polycarbonate as fire retardant at lower concentration.The salt of having found selected aromatic sulfonic acid surprisingly is specially suitable additive, even also is like this when lower concentration.Fire retardant (as fire retardant) as first-selection based on basic metal, alkaline-earth metal or ammonium salt, the salt of the aromatic sulfonic acid of selecting is present in the polycarbonate with small number, and because low dosage level does not have tangible negative impact to polymer machinery and other character.

The present invention relates to composition, fire-retardant combination particularly, it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

a ₁) have the triazinylaminostilbedisulphonic disulphonic acid salt of following formula:

Wherein

R ₁And R ₂Expression-NH independently of one another ₂,-NHC ₁-C ₄Alkyl ,-N (C ₁-C ₄Alkyl) ₂,-NH-hydroxyl C ₂-C ₄Alkyl ,-N (hydroxyl-C ₂-C ₄Alkyl) ₂,-N (C ₁-C ₄Alkyl) (hydroxyl-C ₂-C ₄Alkyl), phenylamino, diphenylamino, by 1-3 be selected from-S (=O) ₂-O ^-M ⁺, C ₁-C ₄Alkyl and C ₁-C ₄Phenylamino or diphenylamino or 5-or 6 Yuans saturated N-heterocyclic radicals (N-heterocyclyl) that the substituting group of alkoxyl group replaces;

R ₁' and R ₂' definition is as R ₁And R ₂With

M ⁺Expression alkali metal atom, ammonium (ammonium) or the positively charged ion that forms by amine;

a ₂) have 2-(2-the hydroxyphenyl)-2H-benzotriazole base sulfonate of following formula:

Wherein

R ₁Expression hydrogen, C ₁-C ₄Alkyl or-S (=O) ₂-O ^-M ⁺Group;

R ₂Expression hydrogen or hydroxyl;

R ₃Expression hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Alkoxyl group or benzyl; With

M ⁺Expression alkali metal atom, ammonium or the positively charged ion that forms by amine;

a ₃) have two-stilbene derivative that the sulfo group phenyl of following formula replaces

Wherein

R ₁And R ₂Represent hydrogen or substituting group independently of one another, this substituting group is selected from-S (=O) ₂-O ^-M ⁺, C ₁-C ₄Alkyl, phenyl-C ₁-C ₄Alkyl, hydroxyl and C ₁-C ₄Alkoxyl group;

R ₁', R ₂' and R ₃' represent independently of one another hydrogen or substituting group, this substituting group be selected from-S (=O) ₂-O ^-M ⁺, C ₁-C ₄Alkyl, phenyl-C ₁-C ₄Alkyl, hydroxyl and C ₁-C ₄Alkoxyl group; With

M ⁺Expression alkali metal atom, ammonium or the positively charged ion that forms by amine; With

a ₄) have that the sulfo group of following formula replaces 2,5-two-(benzoxazolyl)-thiophene derivant:

Wherein

a ₅) have an amphyl that the sulfo group of following formula replaces:

Wherein

R ₁And R ₂Represent hydrogen or substituting group independently of one another, this substituting group is selected from C ₁-C ₄Alkyl, C ₅-C ₆Cycloalkyl, C ₅-C ₆Cycloalkyl-C ₁-C ₄Alkyl, aryl and aryl-C ₁-C ₄Alkyl;

R ₃Expression hydrogen or C ₁-C ₄Alkyl;

X represents C ₂-C ₆Alkylidene group;

Ar represents phenyl, is selected from C by 1 or 2 ₁-C ₄Alkyl, C ₅-C ₆Cycloalkyl, C ₅-C ₆Cycloalkyl-C ₁-C ₄Alkyl, aryl and aryl-C ₁-C ₄The phenyl that the substituting group of alkyl replaces, naphthyl or by 1-4 C ₁-C ₄The naphthyl that alkyl replaces; With

B) M ⁺Expression alkali metal atom, ammonium or the positively charged ion that forms by amine; And polymeric substrate, comprise polycarbonate or polycarbonate Alloys.

Embodiment preferred of the present invention relates to composition, fire-retardant combination particularly, and it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

a ₁) triazinylaminostilbedisulphonic disulphonic acid salt (I), wherein

R ₁And R ₂Expression-NH independently of one another ₂,-N (C ₁-C ₄Alkyl) ₂, be selected from by 1-3-S (=O) ₂-O ^-M ⁺, C ₁-C ₄Alkyl and C ₁-C ₄Phenylamino or 5-or the saturated N-heterocyclic radical of 6-person that the substituting group of alkoxyl group replaces;

R ₁' and R ₂' definition is as R ₁And R ₂With

M ⁺The expression alkali metal atom;

a ₂) 2-(2-hydroxyphenyl)-2H-benzotriazole base sulfonate (II), wherein

R ₁Expression hydrogen;

R ₂Expression hydrogen;

R ₃Expression hydrogen or C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom;

a ₃) two-stilbene derivative (III) of replacing of sulfo group phenyl, wherein

R ₁And R ₂Represent hydrogen or C independently of one another ₁-C ₄Alkyl;

R ₁', R ₂' and R ₃' in one of expression-S (=O) ₂-O ^-M ⁺With other expression hydrogen or C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom;

a ₄) sulfo group replace 2,5-two-(benzoxazolyl)-thiophene derivant (IV), wherein

R ₁', R ₂' and R ₃' represent independently of one another hydrogen or substituting group, this substituting group be selected from-S (=O) ₂-O ^-M ⁺And C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom; With

a ₅) amphyl (V) that replaces of sulfo group, wherein

R ₃Expression hydrogen or C ₁-C ₄Alkyl;

X represents C ₂-C ₆Alkylidene group;

Ar represents phenyl or by 1 or 2 C ₁-C ₄The phenyl that alkyl replaces; With

M ⁺The expression alkali metal atom; With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

A particularly preferred embodiment relates to composition, fire-retardant combination particularly, and it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

a ₁) triazinylaminostilbedisulphonic disulphonic acid salt (I), wherein

R ₁And R ₂Expression-N (C independently of one another ₁-C ₄Alkyl) ₂, by 1 or 2-S (=O) ₂-O ^-M ⁺The phenylamino or the morpholinyl that replace;

R ₁' and R ₂' definition is as R ₁And R ₂With

M ⁺The expression alkali metal atom;

a ₂) 2-(2-hydroxyphenyl)-2H-benzotriazole base sulfonate (II), wherein

R ₁Expression hydrogen or C ₁-C ₄Alkyl;

R ₂Expression hydrogen or hydroxyl;

R ₃Expression hydrogen or C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom; With

a ₅) amphyl (V) that replaces of sulfo group, wherein

R ₁And R ₂In one of expression methyl and another expression tertiary butyl or R ₁And R ₂All represent the tertiary butyl;

R ₃Expression hydrogen or methyl;

X represents C ₂-C ₄Alkylidene group;

Ar represents by 1 methyl and 1 tertiary butyl or the phenyl that replaced by 2 tertiary butyls; With

M ⁺The expression alkali metal atom; With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

A highly preferred embodiment relates to composition, fire-retardant combination particularly, and it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

a ₁) triazinylaminostilbedisulphonic disulphonic acid salt (I), wherein

R ₁And R ₂In one of expression-N (C ₁-C ₄Alkyl) ₂With another the expression by 2-S (=O) ₂-O ^-M ⁺The phenylamino that replaces;

R ₁' and R ₂' definition is as R ₁And R ₂With

M ⁺The expression alkali metal atom;

a ₂) 2-(2-hydroxyphenyl)-2H-benzotriazole base sulfonate (II), wherein

R ₁And R ₂Expression hydrogen; With

R ₃Expression hydrogen or C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom; With

R ₁And R ₂Expression hydrogen;

R ₁', R ₂' and R ₃' in one of expression-S (=O) ₂-O ^-M ⁺With other expression hydrogen; With

M ⁺The expression alkali metal atom;

a ₅) amphyl (V) that replaces of sulfo group, wherein

R ₁And R ₂The expression tertiary butyl;

R ₃Expression hydrogen;

X represents ethylidene;

Ar represents by the phenyl of 2 tertiary butyls replacements; With

M ⁺The expression alkali metal atom; With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

The most preferred embodiment relates to composition, fire-retardant combination particularly, and it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

With

a ₅) have an amphyl that the sulfo group of following formula replaces:

With its salt;

With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

Composition according to the present invention has obtained desirable V-0 grade (according to UL-94 (Underwriter ' s Laboratories Subject 94)) and other good grades in the correlation test method, and keep good machinery, chemistry and the thermal properties of polycarbonate simultaneously, as optical transparency.

Said composition as top definition, comprises following component:

Component a)

Term " salt of aromatic sulfonic acid " preferably includes metal-salt in its scope, for example basic metal or alkaline earth salt, for example sodium, potassium, calcium salt.

According to a selectable embodiment, term " salt " comprises non-metal salt, for example ammonium, (C ₁-C ₂₂Alkyl) _1-4Ammonium or (2-hydroxyethyl) _1-4Ammonium, for example tetramethyl-ammonium, tetraethyl ammonium or 2-hydroxyethyl leptodactyline.

Therefore, the positively charged ion M in the formula in the above ⁺The scope that is defined in it within comprise alkali metal atom, for example, sodium or potassium ion, ammonium ion or the positively charged ion that forms by amine, for example (C ₁-C ₂₂Alkyl) _1-4Ammonium or (2-hydroxyethyl) _1-4Ammonium, for example tetramethyl-ammonium, tetraethyl ammonium or 2-hydroxyethyl trimethyl ammonium ion.

In triazinylaminostilbedisulphonic disulphonic acid salt (I), at R ₁And R ₂Correspondingly at R ₁' and R ₂The C of ' middle existence ₁-C ₄Alkyl be methyl, ethyl, just-propyl group, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl.

Hydroxyl-C ₂-C ₄Alkyl is the 2-hydroxyethyl preferably.

Be selected from by 1-3-S (=O) ₂-O ^-M ⁺, C ₁-C ₄Alkyl and C ₁-C ₄Phenylamino or diphenylamino that the substituting group of alkoxyl group replaces be, for example phenylamino or diphenylamino, wherein phenyl by 1 or 2-S (=O) ₂-O ^-Na ⁺Group or replaced by 1 or 2 methyl or methoxies.

C ₁-C ₄Alkoxyl group be methoxyl group, oxyethyl group, just-propoxy-, isopropoxy, just-butoxy, isobutoxy or tert.-butoxy.

The saturated N-heterocyclic radical of 5-or 6-person for example is, pyrrolidyl, piperidyl or be preferably morpholinyl.

Particularly preferably be

SFP (Ciba Specialty Chemicals): 4,4 '-two (2-amino-4-monoethanolamine amino-6-s-triazinyl)-diamino Stilbene-2,2 '-sodium disulfonate:

Triazinylaminostilbedisulphonic disulphonic acid salt (I) is compound known.They are used as the technology of fluorescent bleaches and their preparation is described among the WO2005/068597.In 2-(2-hydroxyphenyl)-2H-benzotriazole sulfonate (II), at R ₁, R ₂And R ₃The middle M that exists ⁺, C ₁-C ₄Alkyl and C ₁-C ₄The definition of alkoxyl group is corresponding to the definition in compound (I).

Particularly preferably be

HS (Ciba Specialty Chemicals): 3-(2H-benzotriazole-2-yl)-4-hydroxyl-5-(1-methyl-propyl)-benzene sulfonic acid sodium salt:

2-(2-hydroxyphenyl)-2H-benzotriazole base sulfonate (II) is compound known.They are used as the technology of the photostabilizer (photo-stabilisingagents) of anti-light embrittlement (photo-tendering) in textiles and the preparation of these compounds is described among the WO 84/02365.

In two-stilbene derivative (III) that the sulfo group phenyl replaces, at R ₁And R ₂With at R ₁', R ₂' and R ₃The M of ' middle existence ⁺, C ₁-C ₄Alkyl and C ₁-C ₄The definition of alkoxyl group is corresponding to the definition in compound (I).

Phenyl-C ₁-C ₄Alkyl is, for example benzyl or 1-or 2-styroyl.

Particularly preferably be TINOPAL CBS:2,2 '-(4,4 '-biphenyl two bases two-2,1-ethene-two base)-the phenylbenzene disodium sulfonate:

Two-stilbene derivative that the sulfo group phenyl replaces is a compound known.They are used as the technology of white dyes and their preparation is described in US Patent specification No.3, in 984,399.

In the amphyl (V) that sulfo group replaces, R ₁And R ₂Represent hydrogen or substituting group independently of one another, this substituting group is selected from C ₁-C ₄Alkyl, C ₅-C ₆Cycloalkyl, C ₅-C ₆Cycloalkyl-C ₁-C ₄Alkyl, aryl and aryl-C ₁-C ₄Alkyl.

C ₁-C ₄Alkyl be methyl, ethyl, just-or sec.-propyl or just-, the exclusive OR tertiary butyl.

C ₅-C ₆Cycloalkyl is cyclopentyl or cyclohexyl.

C ₅-C ₆Cycloalkyl-C ₁-C ₄Alkyl is, for example cyclopentyl-methyl or cyclohexyl methyl.

Aryl is phenyl preferably.

Aryl-C ₁-C ₄Alkyl is benzyl or 2-styroyl preferably.

R ₃Preferably hydrogen or methyl.

Be defined as C ₂-C ₆The X of alkylidene group is straight chain preferably, for example ethylidene, positive propylidene or positive butylidene.

Be defined as being selected from C by 1 or 2 ₁-C ₄Alkyl, C ₅-C ₆Cycloalkyl, C ₅-C ₆Cycloalkyl-C ₁-C ₄The Ar of the phenyl that the substituting group of alkyl replaces is, for example phenyl that is replaced by 1 methyl and 1 tertiary butyl or the phenyl that is replaced by 2 tertiary butyls, the phenyl that is replaced by cyclopentyl or cyclohexyl, the phenyl that is replaced by benzyl or the phenyl that replaced by cyclopentyl-methyl or cyclohexyl methyl.

By 1-4 C ₁-C ₄The naphthyl that alkyl replaces is, for example naphthyl that replaces by 1-4 methyl substituted naphthyl, by 1 methyl or the 1-tertiary butyl or the naphthyl that is replaced by 2 tertiary butyls.

The amphyl (V) that sulfo group replaces is compound known and can be prepared by known method, as at US Patent specification No.3, and the method for describing in 665,031.

According to an embodiment preferred, the amphyl (V) that sulfo group replaces is represented by following structural formula:

Wherein, R ₁And R ₂In one of the expression methyl, another expression tertiary butyl or R ₁And R ₂All represent the tertiary butyl and M ⁺The expression alkalimetal ion.

According to a particularly preferred embodiment, the amphyl (V) that sulfo group replaces is represented by following structural formula:

It can obtain from Ciba Specialty Chemicals Holding Inc. is commercial (

AO 6).

Components b)

The polymeric substrate that comprises polycarbonate or polycarbonate Alloys can be any grade and can be prepared by any currently known methods.The term " polymer " base material " within its scope, comprise any polycarbonate homopolymer or its multipolymer, as with the multipolymer of polyester.

Polycarbonate is the thermoplastic polymer corresponding to following general formula:

Polycarbonate can obtain by interfacial process or by melt process (catalyzed transesterification).Polycarbonate structurally can be side chain or straight chain and can comprise any sense substituent.Copolycarbonate and polycarbonate Alloys also are within the scope of the invention.Term " polycarbonate " should be interpreted as comprising the blend of multipolymer and other thermoplasticss.The method that is used to prepare polycarbonate is known, for example from US Patent specification No.3,030,331; 3,169,121; 4,130,458; 4,263,201; 4,286,083; 4,552,704; 5,210,268; With 5,606,007.Can use two or more to have the combination of the polycarbonate of different molecular weight.

Preferably can pass through the polycarbonate of the reaction acquisition of bis-phenol (as dihydroxyphenyl propane) and carbonate source.The example of suitable bis-phenol is:

Dihydroxyphenyl propane:

Bisphenol AF:

Bisphenol-ap:

Bisphenol b:

Bisphenol-c:

Bis-phenol E:

Bisphenol F:

Bis-phenol M:

Bis-phenol P:

Bisphenol S:

Bis-phenol TMC:

Bisphenol Z:

4,4 '-(the inferior norcamphyl (norbornylidene) of 2-) two (2, the 6-chlorophenesic acid); Or

Fluorenes-9-bis-phenol:

Carbonate source can be carbonylic halide (carbonyl halide), carbonic ether or haloformate (haloformate).Suitable carbonic ether halogenide (carbonate halides) is phosgene or carbonyl bromide (carbonylbromide).Suitable carbonic ether is dialkyl carbonate (as methylcarbonate or a diethyl carbonate), diphenyl carbonate, carbonic acid phenyl-alkane phenylester (as carbonic acid phenyl-tolyl ester), dialkyl carbonate (as methylcarbonate or diethyl carbonate), carbonic acid two (halobenzene base) ester is (as carbonic acid two (chloro-phenyl-) ester, carbonic acid two (bromophenyl) ester, carbonic acid two (trichlorophenyl) ester or carbonic acid two (trichlorophenyl) ester), carbonic acid two (alkane phenyl) ester (as carbonic acid two (toluene) ester), carbonic acid naphthyl ester, carbonic acid dichloro naphthyl ester and other carbonic ethers.

The additive method details as adding molecular weight regulator, acid acceptor, catalyzer, is disclosed in the above-mentioned reference.

According to other embodiments, the polymeric substrate that comprises polycarbonate or polycarbonate Alloys is a polycarbonate-poly (ester-ether) copolymer, wherein has isophthalate/terephthalate-Resorcinol segment (segments).Above-mentioned polycarbonate is commercially available, for example Lexan

SLX (General Electrics Co.USA).Components b) other polymeric substrates can comprise multiple synthetic polymer in addition with the form of mixture or multipolymer, it comprises polyolefine, polystyrene, polyester, polyethers, polymeric amide, poly-(methyl) acrylate, thermoplastic polyurethane, polysulfones, polyacetal and PVC, comprises appropriate compatilizer.For example, polymeric substrate can comprise thermoplastic polymer in addition, and it is selected from the resin groups of being made up of polyolefine, thermoplastic polyurethane, styrene polymer and their multipolymer.Specific embodiment comprises polypropylene (PP), polyethylene (PE), polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), the poly terephthalic acid cyclohexylidene dimethylene ester (PCTG) of glycol-modification, polysulfones (PSU), polymethylmethacrylate (PMMA), thermoplastic polyurethane (TPU), acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-styrene-acrylic ester (ASA), vinyl cyanide-ethylene-propylene-vinylbenzene (AES), phenylethylene-maleic anhydride (SMA) or high impact polystyrene (HIPS).

The list of suitable synthetic polymer is as follows:

1. the polymkeric substance of monoolefine and diolefin, polypropylene for example, polyisobutene, poly-but-1-ene, poly--4-methylpent-1-alkene, polyvinyl eyclohexane, polyisoprene or polyhutadiene, polymkeric substance with cyclenes, the polymkeric substance of cyclopentenes or norbornylene for example, polyethylene (it randomly can be crosslinked), for example high density polyethylene(HDPE) (HDPE), high-density and High molecular weight polyethylene (HDPE-HMW), high-density and ultrahigh molecular weight polyethylene(UHMWPE) (HDPE-UHMW), medium-density polyethylene (MDPE), new LDPE (film grade) (LDPE), LLDPE (LLDPE), (VLDPE) and (ULDPE).

Polyolefine, promptly the polymkeric substance of the paragraph monoolefine of giving an example in front is preferably polyethylene and polypropylene, can particularly be prepared by the following method by diverse ways:

A) radical polymerization (usually at high pressure and at elevated temperatures).

B) use the catalyzed polymerization of catalyzer of one or more metals of IVb, Vb, VIb or the VIII family comprise periodictable usually.These metals have one or more parts usually, and typically to be can be π-or σ-coordinate oxygen root, halogen, pure root, ester, ether, amine, alkyl, thiazolinyl and/or aryl.These metal complexess can be free states or be fixed on the base material, typically on activation magnesium chloride, titanium chloride (III), aluminum oxide or silicon oxide.These catalyzer can be soluble or insoluble in polymerisation medium.These catalyzer can use separately maybe in polymerization can use other activators, be generally metal alkylide, metal hydride, alkyl metal halide, alkyl metal oxide, for example or Jin and belong to Wan Ji oxane (metal alkyloxanes), wherein said metal is Ia, the IIa of the periodic table of elements and/or the element of IIIa family.Activator can easily carry out modification with other esters, ether and amine or silyl ether group in addition.These catalyst systems are commonly called Phillips type catalyzer (Phillips), Indiana Mobil oil company's catalyzer (Standard Oil Indiana), Ziegler (Natta) catalyzer, TNZ (DuPont), metallocene or single site catalysts (SSC).

2. 1) in the mixture of polymers mentioned, for example polypropylene and polyisobutene, polypropylene and poly mixture (for example PP/HDPE, PP/LDPE) and dissimilar poly mixtures (for example LDPE/HDPE).

Monoolefine and diolefine mutual or with the multipolymer of other vinyl monomers, ethylene/propene copolymer for example, the mixture of LLDPE (LLDPE) and it and new LDPE (film grade) (LDPE), propylene/but-1-ene multipolymer, propylene/isobutylene copolymers, ethene/but-1-ene multipolymer, the ethylene/hexene multipolymer, ethene/methylpentene multipolymer, ethene/heptene multipolymer, ethylene/octene, ethylene/vinyl hexanaphthene multipolymer, ethene/cyclic olefine copolymer (for example, ethene/norbornylene such as COC), ethene/1-olefin copolymer, wherein 1-alkene is that original position produces; The terpolymer of propylene/butadienecopolymer, iso-butylene/isoprene copolymer, ethylene/vinyl tetrahydrobenzene multipolymer, ethylene/alkyl acrylate copolymer, ethylene/methacrylic acid alkyl ester copolymer, ethylene/vinyl acetate copolymer or ethylene/acrylic acid copolymer and their salt (ionomer) and ethene and propylene and diene (as hexadiene, Dicyclopentadiene (DCPD) or ethylidene-norbornylene); Above-mentioned multipolymer each other mixture and with in the above 1) in the mixture of polymers mentioned, for example mixture of polypropylene/ethylene-propylene copolymer, LDPE/ ethylene-vinyl acetate copolymer (EVA), LDPE/ ethylene-acrylic acid copolymer (EAA), LLDPE/EVA, LLDPE/EAA and alternative or random polyalkenes/carbon monoxide multipolymer and they and other polymkeric substance (for example polymeric amide).

4. hydrocarbon resin (C for example ₅-C ₉), comprise their hydrogenation modifier (for example, tackifier) with mixture polyalkylene and starch;

Above-mentioned homopolymer and multipolymer can have three-dimensional arrangement, and it comprises syndyotactic, isotactic, partly isotactic or atactic; Wherein unregulated polymer is preferred.Also comprise the tactic block polymer compound.

5. polystyrene, poly-(p-methylstyrene), poly-(alpha-methyl styrene).

6. the aromatic homopolymers of derived from ethylene base aromatic monomer and multipolymer, it comprises all isomer of vinylbenzene, alpha-methyl styrene, Vinyl toluene, particularly right-Vinyl toluene, all isomer of ethyl styrene, propylstyrene, vinyl xenyl, vinyl naphthalene and vinyl anthracene and their mixture.Homopolymer and multipolymer can have three-dimensional arrangement, and it comprises syndiotaxy, isotaxy, half isotaxy or atactic three-dimensional arrangement; Wherein unregulated polymer is preferred.Also comprise the tactic block polymer compound;

A) comprise the above-mentioned vi-ny l aromatic monomers and the multipolymer of comonomer, this comonomer is selected from ethene, propylene, diene, nitrile, acid, maleic anhydride class, maleimide, vinyl acetate and vinylchlorid or acrylic acid derivative and their mixture, for example phenylethylene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpretation), styrene/methacrylic acid alkyl ester, phenylethylene/butadiene/alkyl acrylate, phenylethylene/butadiene/alkyl methacrylate, phenylethylene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; The mixture of the styrol copolymer of high impact strength and another kind of polymkeric substance (for example polyacrylic ester, diene polymer or ethylene/propylene/diene terpolymers); And cinnamic segmented copolymer such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

B) by 6) in the hydrogenating aromatic polymers that obtains of the polymkeric substance hydrogenation mentioned, comprise especially by hydrogenation random isotactic polystyrene preparation poly-cyclohexyl ethene (polycyclohexylethylene) (PCHE), be commonly called polyvinyl eyclohexane (PVCH).

C) by at 6a) in the hydrogenating aromatic polymers that obtains of the hydrogenation of the polymkeric substance mentioned.Homopolymer and multipolymer can have three-dimensional arrangement, and it comprises syndiotaxy, isotaxy, half isotaxy or atactic structure; Wherein unregulated polymer is preferred.Also comprise the tactic block polymer compound.

7. the graft copolymer of vi-ny l aromatic monomers (as vinylbenzene or alpha-methyl styrene) is for example at the vinylbenzene on the polyhutadiene, vinylbenzene on Polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; Vinylbenzene on polyhutadiene and vinyl cyanide (or methacrylonitrile); Vinylbenzene on polyhutadiene, vinyl cyanide and methyl methacrylate; Vinylbenzene on polyhutadiene and maleic anhydride; Vinylbenzene on polyhutadiene, vinyl cyanide and maleic anhydride or maleimide; Vinylbenzene on polyhutadiene and maleimide; Vinylbenzene on polyhutadiene and alkyl acrylate or alkyl methacrylate; Vinylbenzene on ethylene/propylene/diene terpolymers and vinyl cyanide; Vinylbenzene on polyalkyl acrylate or polyalkyl methacrylate and vinyl cyanide; In the vinylbenzene on the acrylate/butadiene copolymers and vinyl cyanide and they and 6) in the mixture of the multipolymer enumerated, for example be called as the copolymer mixture of ABS, MBS, ASA or AES polymkeric substance.

8. halogen containing polymers, as the multipolymer of the chlorination of sovprene, chlorinated rubber, iso-butylene-dimethyl butadiene and brominated copolymer (halogenated butyl rubber), chlorination or sulphur chlorinatedpolyethylene, ethene and ethylene chloride, Epicholorohydrin all-and multipolymer, the particularly polymkeric substance of Halogen vinyl compound, for example polyvinyl chloride, polyvinylidene chloride, fluorinated ethylene propylene, polyvinylidene difluoride (PVDF), and their multipolymer, as vinylchlorid/vinylidene chloride, vinylchlorid/vinyl acetate or vinylidene chloride/vinyl acetate copolymer.

9. derived from alpha, the polymkeric substance of beta-unsaturated acid and their derivative is as polyacrylic ester and polymethacrylate; Carry out impact modified polymethylmethacrylate, polyacrylamide and polyacrylonitrile with butyl acrylate.

10. 9) monomer mentioned mutual or with other the multipolymer of unsaturated monomer, for example acrylonitrile/butadiene multipolymer, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or vinyl cyanide/vinyl halides multipolymer or vinyl cyanide/alkyl methacrylate/butadiene terpolymer.

11. derived from the polymkeric substance of unsaturated alkohol and amine or their acyl derivative or acetal, for example polyvinyl alcohol, polyvinyl acetate (PVA), polyvinyl stearate, polyvinyl benzoate, polymaleic acid vinyl acetate, polyvinyl butyral acetal, poly-phthalic acid allyl propionate or polyene propyl group trimeric cyanamide; And the multipolymer of they and the top alkene of in 1, mentioning.

12. the homopolymer of cyclic ethers and multipolymer are as the multipolymer of polyalkylene glycol, polyethylene oxide, polyoxy propane or they and diglycidylether.

13. polyacetal comprises the polyoxymethylene of oxyethane as comonomer as polyoxymethylene and those; Polyacetal with thermoplastic polyurethane, acrylate or MBS modification.

14. the mixture of polyphenylene oxide and polyphenylene sulfide and polyphenylene oxide and styrene polymer or polymeric amide.

15. derived from one side hydroxyl-terminated polyether, polyester or polyhutadiene and aliphatic series or the urethane of aromatic polyisocyanate and their precursor on the other hand.

16. polymeric amide and copolyamide, it is derived from diamines and dicarboxylic acid and/or derived from aminocarboxylic acid or corresponding lactam (for example, polymeric amide 4, polyamide 6, polyamide 6/6,6/10,6/9,6/12,4/6,12/12, polymeric amide 11, polymeric amide 12, be the aromatic poly of raw material with m-xylene diamine and hexanodioic acid); Or/and it is the having or do not having elastomerics of terephthalic acid preparation, for example poly--2,4,4 from hexamethylene-diamine and m-phthalic acid as polymeric amide under the properties-correcting agent ,-tri-methyl hexamethylene-terephthaldehyde's acid diamide or poly---the phenylene metaxylylene diamine; And above-mentioned polymeric amide combine with polyolefine, olefin copolymer, ionomer or chemical bond or the elastomeric segmented copolymer of grafted; Perhaps with polyethers for example with the segmented copolymer of polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol; And with the polymeric amide or the copolyamide of EPDM or ABS modification; Polymeric amide (RIM polymeric amide system) with condensation during processing.

17. polyureas, polyimide, polyamide-imide, polyetherimide, polyester-imide, poly-glycolylurea and polybenzimidazole.

18. derived from dicarboxylic acid and glycol and/or derived from the polyester of hydroxycarboxylic acid or corresponding lactone, for example polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid 1,4-dimethyl cyclohexane ester, poly-naphthalic acid alkylidene diol ester (PAN) and poly-hydroxybenzoate, and derived from the block copolymerization polyether ester of hydroxyl-terminated polyether; And with the polyester of polycarbonate or MBS modification.

19. polyketone

20. polysulfones, polyethersulfone and polyetherketone.

21. the blend of above-mentioned polymkeric substance (polyblend), for example PP/EPDM, polymeric amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/ acrylate, POM/ thermoplasticity PUR, PC/ thermoplasticity PUR, POM/ acrylate, POM/MBS, PPO/HIPS, PPO/PA6.6 and multipolymer, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

Component a) is joined components b with the amount of about 0.001-5.0 weight %) in the base material, be preferably 0.01-2.0 weight % and be most preferably 0.04-0.5 weight %.

Further embodiment of the present invention relates to the method that flame retardant resistance is provided to the polymeric substrate that comprises polycarbonate or polycarbonate Alloys, this method comprise in described polymeric substrate add as above the salt of aromatic sulfonic acid of defined selection.

Other components

The invention further relates to composition, except as component defined above a) and b), it comprises other additive, and described additive is selected from so-called anti-dripping agent, polymer stabilizer and other fire retardant, as phosphonium flame retardant, contain nitrogen combustion inhibitor, halogenated fire-retardants and inorganic combustion inhibitor.

According to an embodiment preferred, the present invention relates to composition, it comprises so-called anti-dripping agent in addition as annexing ingredient.

These anti-dripping agents reduce the melt flow of polycarbonate compositions and suppress the formation of drop at high temperature.Multiple references, as US Patent specification No.4,263,201, described in the polycarbonate fire-retardant combination and added anti-dripping agent.

The suitable additive that at high temperature suppresses drop formation comprises glass fibre, polytetrafluoroethylene (PTFE), high temperature elastomer, carbon fiber, granulated glass sphere or the like.

In multiple references, proposed to add polysiloxane with different structure; Referring to US Patent specification No.6,660,787,6,727,302 or 6,730,720.

According to a specific embodiment of the present invention, have (gathering) carbonate products of following formula:

Wherein

R ₁And R ₂Represent the aliphatic group that replaced by fluorine independently of one another;

X ₁And X ₂Represent direct key (direct bond) or C independently of one another ₁-C ₁₂Alkylidene group;

M represents from 1 to 1000 numeral;

R ₅, R ₆, R ₇And R ₈Represent hydrogen, C independently of one another ₁-C ₁₂Alkyl or C ₃-C ₁₂Thiazolinyl (alkenyl); With

Y represents direct key or divalent group, and this divalent group is selected from :-O-,-S-,-SO-,-SO ₂-,

With

Wherein

R _aAnd R _bAll represent hydrogen or halogen; Or

R _aAnd R _bIn one of expression hydrogen and another expression halogen;

R ₃And R ₄Have 1-3 C with forming with their bonded carbon atoms ₁-C ₄Alkyl is as optional substituent C ₅-C ₈-cycloalkylidene (cycloalkylidene group); Or

R ₃And R ₄The aliphatic group, the C that represent hydrogen independently of one another, replaced by fluorine ₁-C ₁₂Alkyl, by the C of carboxyl substituted ₁-C ₁₂Alkyl, C ₂-C ₁₂Thiazolinyl, aryl or have group with lower section chemical formula (partial formula):

Wherein

N represents the numeral of 0-10000; With

X ₂, Y, R ₂, R ₅, R ₆, R ₇And R ₈Define as described above.

As above in defined (gathering) carbonate products (1), substituting group is defined as follows:

R ₁And R ₂Represent the aliphatic group (aliphatic group) that replaced by fluorine independently of one another;

X ₁And X ₂Represent direct key or C independently of one another ₁-C ₁₂Alkylidene group;

M represents from 1 to 1000 numeral;

R ₅, R ₆, R ₇And R ₈Represent hydrogen, C independently of one another ₁-C ₁₂Alkyl or C ₃-C ₁₂Thiazolinyl; With

Y represents direct key or divalent group, and this divalent group is selected from:

-O-,-S-,-SO-,-SO ₂-,

With

Wherein, R _aAnd R _bAll represent hydrogen or halogen; Or

R _aAnd R _bIn one of expression hydrogen and another expression halogen;

R ₃And R ₄Have 1-3 C with forming with their bonded carbon atoms ₁-C ₄Alkyl is as optional substituent C ₅-C ₈-cycloalkylidene; Or

R ₃And R ₄The aliphatic group, the C that represent hydrogen independently of one another, replaced by fluorine ₁-C ₁₂Alkyl, by the C of carboxyl substituted ₁-C ₁₂Alkyl, C ₂-C ₁₂Thiazolinyl, aryl, or as group defined above (A), wherein n represents numeral and the X of 0-10000 ₂, Y, R ₂, R ₅, R ₆, R ₇And R ₈Define as described above.

Be defined as being replaced the R of aliphatic group by fluorine ₁And R ₂Preferably straight chain or side chain or hydrocarbyl group, it comprises at least one fluorine atom and at least one hydrogen atom, for example fluoro-C ₁-C ₂₅Alkyl, or have perfluoroalkyl with the lower section chemical formula:

-(CF ₂) _pF (B)，

Wherein p is the numeral from 1-100.

Fluoro-C ₁-C ₂₅Alkyl is for example single-or difluoromethyl, 2-fluoro ethyl, 3-fluoropropyl, 4-fluorine butyl, 5-fluorine amyl group, 6-fluorine hexyl, 7-fluorine heptyl or five fluorine butyl.

Perfluoroalkyl is derived from perfluor alcohol F (CF ₂) _pThe group of-OH (B), wherein p is 1-50, for example trifluoromethyl (p=1) or pentafluoroethyl group (p=2).Preferred perfluoroalkyl is derived from perfluor alcohol, and wherein p is 5,8,9 or 11.

Be defined as C ₁-C ₁₂The X of alkylidene group ₁And X ₂Be divalent group side chain or non-side chain, for example methylene radical, ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1, the inferior heptyl of 7-, octamethylene, 1, the inferior decyl or 1 of 10-, the inferior dodecyl of 12-.X ₁And X ₂One of preferred definition is C ₁-C ₈Alkylidene group, for example C ₂-C ₈Alkylidene group.X ₁And X ₂Especially preferred definition be C ₂-C ₄Alkylidene group, for example ethylidene.

Be defined as C ₁-C ₁₂The R of alkyl ₅, R ₆, R ₇And R ₈Be straight chain or, if possible, it is branched group, methyl for example, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, the 2-ethyl-butyl, n-pentyl, isopentyl, the 1-methyl amyl, 1, the 3-dimethylbutyl, n-hexyl, 1-methyl hexyl, n-heptyl, different heptyl, 1,1,3, the 3-tetramethyl butyl, the 1-methylheptyl, the 3-methylheptyl, just-octyl group, the 2-ethylhexyl, 1,1,3-trimethylammonium hexyl, 1,1,3,3-tetramethyl-amyl group, n-nonyl, positive decyl, the n-undecane base, 1-methyl undecyl or dodecyl.One of preferred definition is C for example ₁-C ₈Alkyl, for example C ₁-C ₄Alkyl is as methyl.

Be defined as C ₃-C ₁₂The R of thiazolinyl ₅, R ₆, R ₇And R ₈Be straight chain or, if possible, be branched group, for example allyl group, crotyl, 3-butenyl, isobutenyl, just-2,4-pentadienyl, 3-methyl-2-butene base, just-2-octenyl, just-2-laurylene base or different laurylene base.

Be defined as having the part chemical formula The Y methylene radical (CH preferably of divalent group ₂=, R _aAnd R _b=H).According to selectable embodiment, R _aAnd R _bAll represent hydrogen or halogen, for example chlorine or bromine, or R _aAnd R _bIn one of expression hydrogen and another expression halogen.

Be defined as having 1-3 C ₁-C ₄Alkyl is as optional substituent C ₅-C ₈The R of-cycloalkylidene ₃And R ₄Be, for example, cyclopentylidene (cyclopentylidene), methyl cyclopentylidene, dimethyl cyclopentylidene, cyclohexylidene (cyclohexylidene), methyl cyclohexylidene, dimethyl cyclohexylidene, trimethylammonium cyclohexylidene, tertiary butyl cyclohexylidene, inferior suberyl (cycloheptylidene) or inferior ring octyl group (cyclooctylidene).Preferred cyclohexylidene.

Be defined as the R of the aliphatic group that replaced by fluorine ₃And R ₄Be fluoro-C for example as defined above ₁-C ₂₅Alkyl, or above-mentioned perfluoroalkyl (B), wherein p is 1-50.

Be defined as C ₁-C ₁₂The R of alkyl ₃And R ₄With top about R ₅, R ₆, R ₇And R ₈Definition identical.

Be defined as C by carboxyl substituted ₁-C ₁₂The R of alkyl ₃And R ₄Be, for example carboxymethyl or 1-or 2-propyloic.

Be defined as the R of aryl ₃And R ₄Preferably phenyl or 1-or 2-naphthyl.

In group (A), index n represents the numeral of 0-10000, X ₂, Y, R ₂, R ₅, R ₆, R ₇And R ₈Define as described above.

Useful especially is (gathering) carbonate products (1), wherein

X ₁And X ₂Represent C independently of one another ₁-C ₁₂Alkylidene group;

M represents from 1 to 1000 numeral;

R ₅, R ₆, R ₇And R ₈Expression hydrogen;

Y represents divalent group

Wherein, R ₃And R ₄Represent independently of one another hydrogen ,-CF ₃, C ₁-C ₁₂Alkyl, phenyl or group (A), wherein n represents from 0 to 10000 numeral and X ₂, Y, R ₂, R ₅, R ₆, R ₇And R ₈By as top the definition, or R ₃And R ₄With with they bonded carbon atoms, form and have 1-3 C ₁-C ₄Alkyl is as optional substituent cyclohexylidene.

Useful especially still (gathering) carbonate products (1), wherein R ₁And R ₂Represent group (B) independently of one another, wherein p is from 1 to 50 numeral.

What be particularly useful is (gathering) carbonate products (1), and wherein p is from 4 to 15 numeral.

Very usefully (gather) carbonate products (1), wherein

R ₁And R ₂Represent group (B) independently of one another, wherein p is from 1 to 50 numeral;

X ₁And X ₂Represent C independently of one another ₂-C ₈Alkylidene group;

M represents from 1 to 1000 numeral;

R ₅, R ₆, R ₇And R ₈Expression hydrogen; With

Y represents divalent group

Wherein

R ₃Expression hydrogen ,-CF ₃, C ₁-C ₁₂Alkyl, phenyl or group (A), wherein digital n represents from 0 to 10000 numeral and X ₂, Y, R ₂, R ₅, R ₆, R ₇And R ₈By as top the definition, or R ₃And R ₄With they bonded carbon atoms, formation has 1-3 C together ₁-C ₄Alkyl is as optional substituent cyclohexylidene.

Very usefully (gather) carbonate products (1), wherein R ₃And R ₄Represent hydrogen or C independently of one another ₁-C ₄Alkyl; Or R ₃And R ₄,, form cyclohexylidene with they bonded carbon atoms.

Particularly preferred still (gathering) carbonate products (1), wherein m is that from 1 to 50 numeral and n are from 0 to 50 numerals.

(gathering) carbonate products (1) is prepared by currently known methods.Fluorinated alcohols is handled with original position and is obtained 2 of fluorinated alcohols, 4-dinitrophenyl carbonic ether with two (2, the 4-dinitrophenyl) carbonic ether (DNPC).Can separate this derivative, and for example handle separately and handle by hydroxy-end capped dihydroxyphenyl propane oligopolymer with various molecular weight.

People such as Brunelle, Macromolecules1991,24,3035-3044 discloses and has used two (2, the 4-dinitrophenyl) carbonic ether to prepare the dipolymer and the cyclic oligomer of dihydroxyphenyl propane.Linked reaction can also form reagent by carbonic acid ester bond and (carry out as phosgene or carbonyl dimidazoles (carbonyldiimidazole, CDI)).

Preferably fluorinated alcohols is, for example fluorine telomer alcohol (fluorotelomer alcohols).For example, they can be from DuPont or Aldrich conduct BA-L is commercial to be obtained.

Preferred bis-phenol starting material are dihydroxyphenyl propanes and have the compound of following formula for example:

According to a selectable embodiment, add (gathering) carbonate products with following formula:

Wherein, R ₀Represent direct key or divalent group, this divalent group is selected from:

-O-,-S-,-SO-,-SO ₂-and

R ₁And R ₂Expression comprises the group of silicon independently of one another;

R ₃And R ₄The aliphatic group, silicon-containing group, the C that represent hydrogen independently of one another, replaced by fluorine ₁-C ₁₂Alkyl, by the C of carboxyl substituted ₁-C ₁₂Alkyl, C ₂-C ₁₂Thiazolinyl, aryl or have group with the lower section chemical formula:

Or R ₃And R ₄With representing C with their bonded carbon atoms ₅-C ₈-cycloalkylidene or by 1-3 C ₁-C ₄The C that alkyl replaces ₅-C ₈-alkylidene group;

R ₅, R ₆, R ₇And R ₈Represent hydrogen, C independently of one another ₁-C ₁₂Alkyl or C ₃-C ₁₂Thiazolinyl;

X ₁And X ₂Represent direct key, C independently of one another ₁-C ₁₂The C of alkylidene group or middle being inserted with-O- ₄-C ₂₅Alkylidene group;

Y ₁And Y ₂Represent direct key or divalent group independently of one another, this divalent group is selected from :-O-,

With

R ₉And R ₁₀Represent direct key or C independently of one another ₁-C ₄Alkylidene group;

R ₁₁, R ₁₂And R ₁₃Represent hydrogen, C independently of one another ₁-C ₁₂Alkyl or C ₃-C ₁₂Thiazolinyl;

R ₁₄Expression hydrogen, C ₁-C ₁₂Alkyl or silicon-containing group,

M represents from 0 to 10000 numeral; With

N represents from 0 to 10000 numeral.

As above in defined (gathering) carbonate products (2), substituting group is defined as follows:

R ₀Represent direct key or divalent group, this divalent group is selected from: -O-,-S-,-SO-,-SO ₂-and

With

R ₁₄Expression hydrogen, C ₁-C ₁₂Alkyl or silicon-containing group;

M represents from 0 to 10000 numeral; With

N represents from 0 to 10000 numeral.

Silicon-containing group preferably represents to have the group with the lower section chemical formula:

Wherein

R ₁₇, R ₁₈, R ₁₉And R ₂₀Represent C independently of one another ₁-C ₁₂Alkyl, with hydroxyl or the amino C that replaces ₁-C ₁₂Alkyl; The centre is inserted with-the hydroxyl C of O- ₄-C ₁₂Alkyl; Or has a group with the lower section chemical formula

Wherein

R ₂₁Expression C ₁-C ₁₂Alkyl or have group with the lower section chemical formula

R ₂₂, R ₂₃, R ₂₄, R ₂₅, R ₂₆, R ₂₇, R ₂₈And R ₂₉Represent C independently of one another ₁-C ₁₂Alkyl or the C that replaces with hydroxyl or amino ₁-C ₁₂-alkyl;

P represents 0-200; With

Q represents 0-200.

What be particularly useful as silicon-containing group is the group with part chemical formula (D), wherein

R ₁₇, R ₁₈, R ₁₉And R ₂₀Represent methyl independently of one another or have group with the lower section chemical formula

R ₂₁Expression methyl or have group with the lower section chemical formula

R ₂₂, R ₂₃, R ₂₄, R ₂₅, R ₂₆, R ₂₇, R ₂₈And R ₂₉It is methyl; With

P and q represent 0-100 independently of one another.

Useful especially is (gathering) carbonate products (2), wherein

R ₀The expression divalent group

R ₃And R ₄Represent hydrogen, trifluoromethyl, silicon-containing group, C independently of one another ₁-C ₁₂Alkyl, phenyl or group (C); Or

R ₃And R ₄With representing C with their bonded carbon atoms ₅-C ₈-cycloalkylidene or by 1-3 C ₁-C ₄The C that alkyl replaces ₅-C ₈-alkylidene group;

R ₅, R ₆, R ₇And R ₈Be hydrogen;

X ₁And X ₂Represent C independently of one another ₁-C ₁₂The C of alkylidene group or middle being inserted with-O- ₄-C ₂₅Alkylidene group;

With

R ₉And R ₁₀Represent direct key or methylene radical independently of one another;

R ₁₁, R ₁₂And R ₁₃Represent hydrogen, C independently of one another ₁-C ₄Alkyl or C ₃-C ₄Thiazolinyl;

R ₁₄Expression hydrogen or C ₁-C ₁₂Alkyl;

M represents 0-10000; With

N represents 0-10000.

Very usefully (gather) carbonate products (2), wherein

R ₀The expression divalent group

R ₃Expression hydrogen ,-CF ₃, C ₁-C ₁₂Alkyl, phenyl or group (C);

R ₄Expression-CF ₃, C ₁-C ₁₂Alkyl or phenyl; Or

R ₃And R ₄With with they bonded carbon atoms, form C ₅-C ₈-cycloalkylidene or by 1-3 C ₁-C ₄The C that alkyl replaces ₅-C ₈-cycloalkylidene;

R ₅, R ₆, R ₇And R ₈Expression hydrogen;

With

R ₁₄Expression hydrogen or C ₁-C ₁₂Alkyl;

M represents 0-10000; With

N represents 0-10000.

Also usefully (gather) carbonate products (2), wherein

R ₃And R ₄Represent hydrogen or C independently of one another ₁-C ₄Alkyl; Or

R ₃And R ₄With forming cyclohexylidene with their bonded carbon atoms.

Preferably (gather) carbonate products (2), wherein X ₁And X ₂Represent C independently of one another ₂-C ₈The C of alkylidene group or middle being inserted with-O- ₄-C ₂₅Alkylidene group.

Further preferably (gather) carbonate products (2), wherein m represents 0-100, and n represents 0-100.

Very usefully (gather) carbonate products (2), wherein

R ₀The expression divalent group

R ₃And R ₄Represent C independently of one another ₁-C ₄Alkyl; Or

R ₃And R ₄With forming cyclohexylidene with their bonded carbon atoms;

R ₅, R ₆, R ₇And R ₈Expression hydrogen;

X ₁And X ₂Represent C independently of one another ₂-C ₄The C of alkylidene group or middle being inserted with-O- ₄-C ₂₅Alkylidene group;

With

M represent 0-100 and

N represents 0-100.

C in (gathering) carbonate products (2) ₁-C ₁₂Alkyl is a straight chain, or if possible, branched-chain alkyl, it is identical with top definition about (gathering) carbonate products (1).

Be defined as C by carboxyl substituted ₁-C ₁₂The R of alkyl ₃And R ₄Preferably carboxymethyl or 1-or 2-propyloic.

Be defined as the R of aryl ₃And R ₄Preferably represent phenyl or by 1-3 C ₁-C ₄The phenyl that alkyl (for example, methyl) replaces.

Be defined as C ₂-C ₁₂The R of thiazolinyl ₃, R ₄, R ₅, R ₆, R ₇And R ₈The expression straight chain, or if possible, the thiazolinyl of side chain, it is identical with top definition about (gathering) carbonate products (1).

Be defined as C ₅-C ₈-cycloalkylidene or by 1-3 C ₁-C ₄The C that alkyl replaces ₅-C ₈The R of-cycloalkylidene ₃And R ₄Be defined as top definition about (gathering) carbonate products (1).

Be defined as C ₁-C ₁₂The X of alkylidene group ₁And X ₂Be defined as C ₁-C ₄The R of alkylidene group ₉And R ₁₀The expression straight chain, or if possible, the alkylidene group of side chain is as top definition about (gathering) carbonate products (1).

Be defined as the C of middle being inserted with-O- ₄-C ₂₅The X of alkylidene group ₁And X ₂Be straight chain or, if possible, be side chain, for example-CH ₂CH ₂-O-CH ₂CH ₂-,-CH ₂CH ₂CH ₂-O-CH ₂CH ₂-,-CH ₂CH ₂CH ₂-O-CH ₂CH ₂CH ₂-or-CH ₂CH ₂-O-CH ₂CH ₂-O-CH ₂CH ₂-.

With hydroxyl or the amino C that replaces ₁-C ₁₂Alkyl is, for example methylol, 1-or 2-hydroxyethyl, aminomethyl or 1-or 2-aminoethyl.

Hydroxyl-C of middle being inserted with-O- ₄-C ₁₂Alkyl is, for example-and CH ₂CH ₂-O-CH ₂CH ₂OH or-CH ₂CH ₂-O-CH ₂CH ₂-O-CH ₂CH ₂OH.

Fluoro-containing group is side chain or the group of non-side chain, and it comprises at least one fluorine atom, for example fluoro-C ₁-C ₂₅Alkyl; Or group (B), wherein p is 1-50.

Fluoro-C ₁-C ₂₅Alkyl is, for example perfluoroalkyl, methyl fluoride, 2-fluoro ethyl, 3-fluoropropyl, 4-fluorine butyl, 5-fluorine amyl group, 6-fluorine hexyl, 7-fluorine heptyl, difluoromethyl, trifluoromethyl, pentafluoroethyl group, five fluorine butyl.

(gathering) carbonate products (2) can obtain by currently known methods.Silanol (silicon alcohol) is handled with two (2, the 4-dinitrophenyl) carbonic ether (DNPC) and is obtained 2 of this silanol with original position, 4-dinitrophenyl carbonic ether.Can separate this derivative and for example handle individually by hydroxy-end capped dihydroxyphenyl propane oligopolymer with various molecular weight.People such as Brunelle, Macromolecules 1991,24, and 3035-3044 discloses and has used two (2, the 4-dinitrophenyl) carbonic ether to prepare the dipolymer and the cyclic oligomer of dihydroxyphenyl propane.Linked reaction can also form agent by carbonic acid ester bond, implements as phosgene or carbonyl dimidazoles (CDI).

Particularly preferred silicon-containing group is derived from monohydroxy polysiloxane, wherein p=10; Polysiloxane, wherein p=64; Seven methyl trisiloxanes of polyalkylene oxide modification; Or 3-(polyoxyethylene) propyl group seven methyl trisiloxanes.Representational structural formula shows below::

Preferred bis-phenol starting material with above-mentioned about prepare that (gathering) carbonate products (1) mentions those are identical.

With about 0.01-5.0 weight %, preferably the amount of 0.25-1.0 weight % joins components b with (gathering) carbonate products (1) or (2)) base material in.Suggestion adds the mixture of (gathering) carbonate products (1) or (2).

According to another embodiment, the present invention relates to comprise in addition the composition of other additives, described other additive is selected from polymer stabilizer and other fire retardants.

Stablizer preferably not halogen-containing and be selected from nitryl stablizer, nitrone stablizer, amine oxide stablizer, benzofuranone stabilization agent, phosphorous acid ester and phosphinate stablizer, quinone methides stablizer and 2,2 '-mono acrylic ester of alkylidene group (alkylidene) two phenol stabilizers.

Other fire retardant is that known component, commodity or they can obtain by known method.

Except in the above about components b) defined those, representational phosphonium flame retardant for example is:

Tetraphenyl Resorcinol diphosphites (

RDP, Akzo Nobel), four (methylol) Phosphonium sulfide, triphenylphosphate, diethyl-N, the hydroxy alkyl ester of the acid of N-two (2-hydroxyethyl)-aminomethyl phosphonic acid ester, phosphorus, ammonium polyphosphate (APP) or (

AP750), resorcinol diphosphate oligopolymer (RDP), phosphonitrile fire retardant and quadrol diphosphate (EDAP).

Containing nitrogen combustion inhibitor for example is, the isocyanuric acid ester fire retardant is as the ester or the isocyanuric acid ester of poly-isocyanurate (polyisocyanurate), isocyanuric acid.Representational embodiment is the isocyanuric acid hydroxy alkyl ester, as three (2-hydroxyethyl) isocyanuric acid ester, three (methylol) isocyanuric acid esters, three (3-hydroxyl-n-propyl) isocyanuric acid ester or triglycidyl group isocyanuric acid esters.

Contain nitrogen combustion inhibitor and comprise the trimeric cyanamide based flameproofing.Representational example is: melamine cyanurate (melamine cyanurate), melamine borate salt (melamine borate), melamine phosphate (melamine phosphate), melamine polyphosphate (melaminepolyphosphate), melamine pyrophosphate (melamine pyrophosphate), trimeric cyanamide ammonium polyphosphate (melamine ammonium polyphosphate) and trimeric cyanamide ammonium pyrophosphate (melamine ammonium pyrophosphate).

Other examples are: benzoguanamine, three (hydroxyethyl) isocyanuric acid ester, wallantoin, glycoluril, melamine cyanurate, melamine phosphate, two (trimeric cyanamide) phosphoric acid salt, melamine pyrophosphate, urea cyanurate (urea cyanurate), melamine polyphosphate, melamine borate salt, ammonium polyphosphate, trimeric cyanamide ammonium polyphosphate or trimeric cyanamide ammonium pyrophosphate, melem (melem), melam (melam), condensation product and/or the senior condensation compound of trimeric cyanamide and phosphoric acid or condensation product and the reaction product of phosphoric acid or their mixture of reaction product and/or trimeric cyanamide of the trimeric cyanamide of melon (melon) series.

Especially should be emphasized that: two (trimeric cyanamide) pyrophosphate salt (dimelaminepyrophosphate), melamine polyphosphate, melem poly-phosphate, melam poly-phosphate, and/or the mixed polymerization salt of the above-mentioned type (mixed polysalt), more particularly be melamine polyphosphate.

Representational organic halogen fire retardant is, for example:

Polybromodiphenyl ether (DE-60F, Great Lakes Corp.), decabromodiphynly oxide (DBDPO;

102E), three [3-bromo-2,2-two (brooethyl) propyl group] phosphoric acid ester ( FMCCorp.), tricresyl phosphate (2, the 3-dibromopropyl) ester, tricresyl phosphate (2,3-two chloropropyls) ester, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalate, many-β-chloroethyl tri methylene phosphonic acid ester mixture (poly-β-chloroethyl triphosphonate mixture), tetrabromo-bisphenol two (2,3-dibromopropyl ether) (PE68), brominated epoxy resin, ethylidene-two (tetrabromo phthalimide) (

BT-93), two (hexachlorocyclopentadiene also) cyclooctane (bis (hexachlorocyclopentadieno) cyclooctane) (DECLORANE

), chlorinated paraffin, octabromodiphenyl base ether, hexachlorocyclopentadiene derivative, 1,2-two (tribromophenoxy) ethane (FF680), tetrabromo-dihydroxyphenyl propane (

RB100), ethylene (two bromo-norbornane dicarboximides (norbornanedicarboximide)) (

BN-451), two (chlordene cyclopenta) cyclooctane, PTFE, three (2, the 3-dibromopropyl)-isocyanuric acid ester and ethylidene-two-tetrabromo-phthalic diformazan acid diamide.

Above-mentioned fire retardant normally combines with the inorganic oxide synergistic agent.Be used for this purposes the most common be zinc or sb oxide, Sb for example ₂O ₃Or Sb ₂O ₅Boron compound also is suitable.

Above-mentioned other fire retardant kind advantageously is comprised in the composition of the present invention with the amount of about 0.5%-about 45.0% of organic polymer base material weight; For example be about 1.0%-about 40.0% of polymer weight; For example be about 5.0%-about 35.0%.

As mentioned above, the additive that can comprise one or more routine according to composition of the present invention in addition, for example be selected from pigment, dyestuff, softening agent, antioxidant, thixotropic agent, leveling auxiliary agent (levelling assistants), the alkalescence co-stabilizer, metal passivator, metal oxide, organo phosphorous compounds, other photostabilizers and their mixture, be pigment especially, phenol antioxidant, calcium stearate, Zinic stearas, 2-hydroxyl-benzophenone, 2-(2 '-hydroxyphenyl) benzotriazole and/or 2-(2-hydroxyphenyl)-1,3, the UV absorption agent of 5-triazines.More specific example is following component:

1. antioxidant

Alkylating monophenol, for example 2,6 di tert butyl 4 methyl phenol, the 2-tertiary butyl-4,6-xylenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,6-di-t-butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4,6-xylenol, 2, the two octadecyls of 6--4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-di-t-butyl-4-methoxymethyl phenol, in side chain the nonylphenol of straight or branched, for example 2,6-two-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methyl undecane-1 '-yl) phenol, 2,4-dimethyl-6-(1 '-methyl heptadecane-1 '-yl) phenol, 2,4-dimethyl-6-(1 '-methyl tridecane-1 '-yl) phenol and its mixture.

Alkyl sulfide ylmethyl phenol, for example 2,4-dioctyl sulfenyl methyl-6-tert butyl phenol, 2,4-dioctyl sulfenyl methyl-6-methylphenol, 2,4-dioctyl sulfenyl methyl-6-ethylphenol, 2,6-two-dodecyl sulfenyl methyl-4-nonylphenol.

Quinhydrones and alkylation quinhydrones, for example 2,6-di-t-butyl-4-methoxyphenol, 2, the 5-di-tert-butyl hydroquinone, 2,5 di tert amlyl hydroquinone, 2,6-phenylbenzene-4-octadecane oxygen base phenol, 2, the 6-di-tert-butyl hydroquinone, 2,5-di-t-butyl-4-BHA, 3,5-di-t-butyl-4-BHA, stearic acid 3,5-di-t-butyl-4-hydroxyphenyl ester, two (3,5-di-t-butyl-4-hydroxyphenyl) adipic acid ester.

Tocopherol, for example α-, β-, Gamma-Tocopherol, Delta-Tocopherol and its mixture (vitamin-E).

Hydroxylation sulfenyl phenyl ether, for example 2,2 '-sulfenyl two (the 6-tertiary butyl-4-methylphenol), 2,2 '-sulfenyl two (4-octyl phenol), 4,4 '-sulfenyl two (the 6-tertiary butyl-3-methylphenol), 4,4 '-sulfenyl two (the 6-tertiary butyl-2-methylphenol), 4,4 '-sulfenyl two (3,6-two-sec.-amyl sec-pentyl secondary amyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxyphenyl) disulphide.

The alkylidene bisphenols class, for example 2,2 '-methylene-bis (the 6-tertiary butyl-4-methylphenol), 2,2 '-methylene-bis (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene-bis [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol], 2,2,2 '-methylene-bis (6-nonyl-4-methylphenol), 2,2 '-methylene-bis (4, the 6-DI-tert-butylphenol compounds), 2,2 '-ethylenebis (4, the 6-DI-tert-butylphenol compounds), 2,2 '-ethylenebis (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene-bis [6-(α-Jia Bianji)-4-nonylphenol], 2,2 '-methylene-bis [6-(α, α-Er Jiajibianji)-the 4-nonylphenol], 4,4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene-bis (the 6-tertiary butyl-2-methylphenol), 1, two (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane of 1-, 2, two (the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-methylphenols of 6-, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1, two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-3-dodecyl sulfydryl butane of 1-, ethylene glycol bis [3,3-pair (3 '-tertiary butyl-4 '-hydroxyphenyl) butyric ester], two (3-tertiary butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, two [2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-xylyl)-the 6-tertiary butyl-4-aminomethyl phenyl] terephthalate, 1,1-pair-(3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-two (3,5-di-t-butyl-4-hydroxyphenyl) propane, 2,2-pair-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-4-dodecyl sulfydryl butane, 1,1,5,5-four (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane.

O-, N-and S-benzyl compounds class, for example 3,5,3 ', 5 '-tetra-tert-4,4 '-the dihydroxyl dibenzyl ether, octadecyl-4-hydroxyl-3,5-dimethyl benzyl mercaptoacetate, tridecyl-4-hydroxyl-3,5-di-t-butyl benzyl mercaptoacetate, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) amine, two (4-tertiary butyls-3-hydroxyl-2, the 6-dimethyl benzyl) disulfide group terephthalate, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide, iso-octyl-3,5-di-tert-butyl-4-hydroxyl benzyl mercaptoacetate.

Acrinyl malonic ester class, for example two octadecyls-2,2-two (3,5-di-t-butyl-2-hydroxybenzyl) malonic ester, two octadecyl-2-(3-tertiary butyl-4-hydroxy-5-xylyl) malonic ester, two dodecyl mercaptoethyls-2,2-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) malonic ester, it is two that [4-(1,1,3, the 3-tetramethyl butyl) phenyl]-2, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) malonic esters of 2-.

Aromatics acrinyl compounds, for example 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,4,6-trimethylbenzene, 1, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,3,5 of 4-, 6-durene, 2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) phenol.

The triaizine compounds class, for example 2, two (octyl group the sulfydryl)-6-(3,5-di-t-butyl-4-hydroxybenzene amido)-1 of 4-; 3, the 5-triazine, 2-octyl group sulfydryl-4,6-two (3; 5-di-t-butyl-4-hydroxybenzene amido)-and 1,3,5-triazines, 2-octyl group sulfydryl-4; two (3,5-di-t-butyl-4-the hydroxyphenoxy)-1,3,5-triazines of 6-; 2,4,6-three (3,5-di-t-butyl-4-hydroxyphenoxy)-1; 2,3-triazine, 1,3; 5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, 2,4; 6-three (3,5-di-t-butyl-4-leptodactyline)-1,3,5-triazines; 1,3,5-three (3,5-di-tert-butyl-hydroxy phenyl propionyl)-six hydrogen-1; 3,5-triazine, 1; 3,5-three (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanuric acid ester.

Benzylphosphonic acid ester class, dimethyl-2 for example, 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, diethyl-3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, two octadecyls-3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester, two octadecyls-5-tertiary butyl-4-hydroxy-3-methyl-benzyl phosphonic acid ester, 3, the calcium salt of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic mono ethyl ester.

The acyl amino phenols, 4-hydroxyl lauroyl aniline for example, 4-hydroxyl stearanilide, N-(3,5-di-t-butyl-4-hydroxyphenyl) carboxylamine octyl group ester.

The ester of β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid, what constitute ester group is monohydroxy or poly-hydroxy alcohols, for example methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1,6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, sulfenyl glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxyethyl) ester, N, N '-two (hydroxyethyl) oxamide, 3-thia (thia-) hendecanol, 3-thia (thia-) pentadecylic alcohol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring [2.2.2] octanes are as can the commercial product that obtains, as Irganox

1076.

The ester of β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid, what constitute ester group is monohydroxy or poly-hydroxy alcohols, for example methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1, the 6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, the sulfenyl glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxyethyl) ester, N, N '-two (hydroxyethyl) oxamide, 3-thia (thia-) hendecanol, 3-thia (thia-) pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring [2.2.2] octanes; 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5.5] undecane.

The ester of β-(3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid, the monohydroxy or the poly-hydroxy alcohols that constitute ester group are for example methyl alcohol, ethanol, octanol, stearyl alcohol, 1,6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, sulfenyl glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxyethyl) ester, N, N '-two (hydroxyethyl) oxamide, 3-thia (thia-) hendecanol, 3-thia (thia-) pentadecylic alcohol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring [2.2.2] octanes.

3, the ester class of 5-di-tert-butyl-hydroxy phenyl acetate, the monohydroxy or the poly-hydroxy alcohols that constitute ester group are for example methyl alcohol, ethanol, octanol, stearyl alcohol, 1,6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, sulfenyl glycol ether, glycol ether, triglycol, tetramethylolmethane, isocyanuric acid three (hydroxyethyl) ester, N, N '-two (hydroxyethyl) oxamide, 3-thia (thia-) hendecanol, 3-thia (thia-) pentadecylic alcohol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa two ring [2.2.2] octanes.

The acid amides of β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid, for example N; N '-two (3,5-di-tert-butyl-hydroxy phenyl propionyl) adipamide, N; N '-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) Malonamide, N, N '-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine; N, N '-two [2-(3-[3,5-di-t-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (

XL-1 is provided by Uniroyal).

Xitix (vitamins C)

2. photostabilizer

2-(2 '-hydroxy phenyl) benzotriazole category, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole for example, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-(1,1,3, the 3-tetramethyl butyl) benzotriazole phenyl), 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-the 5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(3 '-sec-butyl-the 5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(3 ', 5 '-two tert-pentyls-2 '-hydroxy phenyl) benzotriazole, 2-(3 ', 5 '-two (α, α-Er Jiajibianji)-2 '-and hydroxy phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-carbonyl octyloxy ethyl) phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) carbonyl ethyl]-2 '-hydroxy phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-carbonyl octyloxy ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) carbonyl ethyl]-2 '-hydroxy phenyl) benzotriazole, 2-(3 '-dodecyl-2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the different carbonyl octyloxy ethyl of 2-) phenyl benzotriazole, 2, [4-(1 for 2 '-methylene radical two, 1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-y1 phenol]; The 2-[3 '-tertiary butyl-5 '-(2-methoxycarbonyl ethyl)-2 '-hydroxy phenyl]-product of transesterification reaction of 2H-benzotriazole and Liquid Macrogol;

, R=3 '-tertiary butyl-4 '-hydroxyl-5 '-2H-benzotriazole-2-base phenyl wherein, 2-[2 '-hydroxyl-3 '-(α, α-Er Jiajibianji)-5 '-(1,1,3, the 3-tetramethyl butyl) phenyl] and benzotriazole; 2-[2 '-hydroxyl-3 '-(1,1,3, the 3-tetramethyl butyl)-5 '-(α, α-Er Jiajibianji) phenyl] benzotriazole, as can from The commercial photostabilizer that obtains of series, as TINUVIN 234,326,329,350,360 or TINUVIN 1577.

2-hydroxy benzophenone ketone, 4-hydroxyl for example, 4-methoxyl group, 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base, 4-dodecyloxy, 4-benzyl oxygen base, 4,2 ', 4 '-trihydroxy-and 2 '-hydroxyl-4,4 '-dimethoxy derivative.

Replace and unsubstituted benzoic ester; Whitfield's ointment 4-tert-butyl-phenyl ester for example; the Whitfield's ointment phenylester; Whitfield's ointment octyl phenyl ester; dibenzoyl resorcinols, two (4-tert.-butylbenzene formyl radical) Resorcinol, benzoyl Resorcinol; 3; 5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butyl-phenyl ester, 3; 5-di-tert-butyl-4-hydroxybenzoic acid cetyl ester; 3,5-di-tert-butyl-4-hydroxybenzoic acid stearyl, 3; 5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-tert-butyl-phenyl ester.

Acrylate, alpha-cyano-β for example, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenyl 2-Propenoic acid-2-ethylhexyl ester, α-methoxycarbonyl methyl cinnamate, alpha-cyano-Beta-methyl-right-p-Methoxymethylcinnamate, alpha-cyano-Beta-methyl-right-methoxy cinnamic acid butyl ester, α-methoxycarbonyl-right-p-Methoxymethylcinnamate and N-(beta-carbomethoxy-3-beta-cyano vinyl)-2-methyl indoline.

Nickel compound; for example 2; [4-(1 for 2 '-sulphur two; 1; 3,3-tetramethyl butyl) phenol] nickel complex, as 1:1 or 1:2 title complex; be with or without other parts (as just-butylamine; trolamine or N-cyclohexyl diethanolamine), nickel dibutyl dithiocarbamate, mono alkyl ester; 4-hydroxyl-3 for example; the methyl esters of 5-di-t-butyl benzylphosphonic acid or the nickel salt of ethyl ester, the nickel complex of ketoxime, for example nickel complex of 2-hydroxy-4-methyl phenyl undecyl ketoxime; the nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazoles is with or without other parts.

Oxamides, for example 4,4 '-two octyloxy oxanilides, 2,2 '-diethoxy oxanilide, 2,2 '-two octyloxies-5,5 '-two tert.-butoxy oxanilides (di-tert-butoxanilide), 2,2 '-two dodecyloxies-5,5 '-two tert.-butoxy oxanilides, 2-oxyethyl group-2 '-ethyl oxanilide, N, N '-two (3-dimethylaminopropyl) oxamide, the 2-oxyethyl group-5-tertiary butyl-2 '-oxyethyl group oxanilide (ethoxanilide) and itself and 2-oxyethyl group-2 '-ethyl-5, the mixture of 4 '-two tert.-butoxy oxanilides, adjacent-and the mixture of right-methoxyl group-dibasic oxanilide and neighbour-and the mixture of right-oxyethyl group-dibasic oxanilide.

2-(2-hydroxy phenyl)-1,3,5-triazines, for example 2,4,6-three (2-hydroxyl-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2, the 4-dihydroxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2,4-two (2-hydroxyl-4-propoxy-phenyl)-6-(2, the 4-3,5-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4,6-two (4-aminomethyl phenyl)-1,3,5-triazine, 2-(2-hydroxyl-4-dodecyloxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-tridecane oxygen base phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy propoxy-) phenyl]-4,6-two (2, the 4-dimethyl)-1,3, the 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy propoxy-) phenyl]-4,6-two (2, the 4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecane oxygen base-2-hydroxyl propoxy-)-2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-dodecyloxy propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-hexyloxy) phenyl-4,6-phenylbenzene-1,3, the 5-triazine, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4,6-phenylbenzene-1,3, the 5-triazine, 2,4,6-three [2-hydroxyl-4-(3-butoxy-2-hydroxyl propoxy-) phenyl]-1,3, the 5-triazine, 2-(2-hydroxy phenyl)-4-(4-p-methoxy-phenyl)-6-phenyl-1,3, the 5-triazine, 2-{2-hydroxyl-4-[3-(2-ethylhexyl-1-oxygen base)-2-hydroxyl propoxy-] phenyl }-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine.

3. metal passivator; N for example; N '-phenylbenzene oxamide, N-salicylic aldehyde-N '-salicylyl hydrazine, N, N '-two (salicylyl) hydrazine, N, N '-two (3; 5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine, 3-salicylyl amino-1; 2,4-triazole, two (benzylidene) oxalyl two hydrazines, oxanilide, m-p-hthaloyl dihydrazide, sebacoyl phenylbenzene hydrazides, N, N '-di-acetyl adipyl dihydrazide, N; N '-two (salicylyl) oxalyl two hydrazines, N, N '-two (salicylyl) sulfenyl propionyl two hydrazines.

4. other phosphorous acid ester and phosphinate (phosphonite), triphenyl phosphite for example, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, three (nonyl phenyl) phosphorous acid ester, three (lauryl) phosphorous acid ester, three (octadecyl) phosphorous acid ester, distearyl pentaerythrityl diphosphite, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, the diiso decyl pentaerythritol diphosphites, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,4-two-cumyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, diiso decyl oxygen base pentaerythritol diphosphites, two (2,4-di-t-butyl-6-aminomethyl phenyl) pentaerythritol diphosphites, two (2,4,6-three (tert-butyl-phenyl) pentaerythritol diphosphites, three stearyl Sorbitol Powder GW-540s, four (2, the 4-di-tert-butyl-phenyl) 4,4 '-the biphenylene bisphosphonates, 6-iso-octyl oxygen base-2,4,8,10-tetra-tert-12H-hexichol [d, g]-1,3,2-two oxa-phosphorus heterocycle octenes, two (2,4-di-t-butyl-6-aminomethyl phenyl) methyl phosphorous acid ester, two (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester, 6-fluoro-2,4,8,10-tetra-tert-12-methyl-hexichol [d, g]-1,3,2-two oxa-phosphorus heterocycle octenes, 2,2 ', 2 ＂-nitrilo [triethyl three (3,3 ', 5,5 '-tetra-tert-1,1 '-biphenyl-2,2 '-two bases) phosphorous acid ester], 2-ethylhexyl (3,3 ', 5,5 '-tetra-tert-1,1 '-biphenyl-2,2 '-two bases) phosphorous acid ester, 5-butyl-5-ethyl-2-(2,4, the 6-tri-butyl-phenoxy)-1,3,2-two oxa-phosphorus heterocycle propane.

Following phosphorous acid ester is especially preferred:

Three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (

168, Ciba SpecialtyChemicals), three (nonyl phenyl) phosphorous acid ester,

5. other nitrone, N-benzyl-alpha-phenyl nitrone for example, N-ethyl-Alpha-Methyl-nitrone, N-octyl group-α-heptyl-nitrone, N-lauryl-α-undecyl-nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl nitrone, derived from N, the nitrone of N-dialkyl group oxyamine (it is derived from hydrogenated tallow amine).

6. sulfenyl synergistic agent, for example Tyox B or distearylthiodi-propionate.

7. peroxide scavenger, the ester class of β-thio-2 acid for example, for example lauryl, stearyl, tetradecyl or tridecyl ester class, the zinc salt of mercaptobenzimidazole or 2-mercaptobenzimidazole, dibutyl disulfide group carbaminate, two (octadecyl) disulfide, four (β-dodecyl sulfydryl) propionic acid pentaerythritol ester.

8. polymeric amide stablizer is for example with iodide and/or phosphorus compound bonded mantoquita and manganous salt.

9. alkaline co-stabilizer, trimeric cyanamide for example, polyvinylpyrrolidone, Dyhard RU 100, triallyl cyanurate, urea derivatives, polymeric amide, urethane, an alkali metal salt of higher fatty acid and alkaline earth salt, calcium stearate for example, Zinic stearas, docosoic acid magnesium, Magnesium Stearate, sodium ricinoleate and potassium palmitate, pyrocatechol (pyrocatecholate) antimony or pyrocatechol (pyrocatecholate) zinc.

10. nucleator, inorganic substance for example, as talcum, metal oxide-type such as titanium dioxide or magnesium oxide, the phosphoric acid salt of preferred bases earth metals, carbonate or vitriol; The salt of organic compound such as list or multi-carboxylic acid and they, 4-p t butylbenzoic acid for example, hexanodioic acid, diphenyl acetic acid, sodium succinate or Sodium Benzoate; Polymerizable compound such as ionic copolymer (" ionomer ").Especially preferred is 1,3:2, two (3 ', the 4 '-dimethyl benzal base) Sorbitol Powders of 4-, 1,3:2,4-two (to methyl two benzal bases) Sorbitol Powder and 1,3:2,4-two (benzal base) Sorbitol Powder.

11. other filler and toughener, lime carbonate for example, silicate, glass fibre, granulated glass sphere, Stainless Steel Fibre, aramid fiber, asbestos, talcum, kaolin, mica, barium sulfate, metal oxide and oxyhydroxide, carbon black, graphite, the powder or the fiber of wood powder and other natural product, synthon.

12. other additive, for example blend compatilizer, softening agent, lubricant, emulsifying agent, pigment, auxiliary rheological agents, catalyzer, flowing regulator, white dyes, flame-proofness, static inhibitor and whipping agent.

13. other Benzopyranone kind (benzofuranones) and indoline ketone (indolinones) for example are disclosed in US Patent specification No.4,325,863; 4,338,244; 5,175,312; 5,216,052 or US5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; Among EP-A-0589839 or the EP-A-0591102 those or 3-[4-(2-acetoxyethoxy) phenyl]-5,7-di-t-butyl benzo furans-2-ketone, 5,7-di-t-butyl-3-[4-(2-stearoyl keto base oxethyl) phenyl] cumarone-2 ketone, 3,3 '-two [5,7-di-t-butyl-3-(the 4-[2-hydroxyl-oxethyl] phenyl) cumarone-2 ketone], 5,7-di-t-butyl-3-(4-phenelyl) benzofuran-2-ones, 3-(4-acetoxy-3,5-3,5-dimethylphenyl)-5,7-di-t-butyl-benzofuran-2-ones, 3-(3,5-dimethyl-4-new pentane acyloxy phenyl)-5,7-di-t-butyl-benzofuran-2-ones, 3-(3, the 4-3,5-dimethylphenyl)-5,7-di-t-butyl-benzofuran-2-ones, 3-(2, the 3-3,5-dimethylphenyl)-5,7-di-t-butyl-benzofuran-2-ones.

Other additives that preferably are used for as top defined composition are processing stabilizers (processing stabilizers) (as above-mentioned phosphorous acid ester and phenol antioxidant) and photostabilizer (as benzotriazole category).Preferred special antioxidants comprises 3-(3,5-two-tertiary butyl-4-hydroxyphenyl)-propionic acid stearyl (IRGANOX 1076).Specific processing stabilizers comprises three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (IRGAFOS 168) and four (2, the 4-di-tert-butyl-phenyl) [1, the 1-phenylbenzene]-4,4 '-two basic two phosphinates (IRGAFOSP-EPQ).Specific photostabilizer comprises 2-(2H-benzotriazole-2-yl)-4,6-two (1-methyl isophthalic acid-styroyl) phenol (TINUVIN 234), 2-(5-chlorine (2H)-benzotriazole-2-yl)-4-(methyl)-6-(tertiary butyl) phenol (TINUVIN 326), 2-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol (TINUVIN 329), 2-(2H-benzotriazole-2-yl)-4-(tertiary butyl)-6-(sec-butyl) phenol (TINUVIN 350), 2,2 '-methylene radical two (6-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol) (TINUVIN 360) and 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-and the 5-[(hexyl) the oxygen base]-phenol (TINUVIN 1577).

With respect to polymeric constituent b) weight, additive above-mentioned preferably packet content is 0.01%-10.0%, especially is 0.05%-5.0%.

By known method (as the dry blending of powder type, or for example the wet mixing of the solution in inert solvent, water or oil, dispersion or form of suspension is closed) binder component a) is joined polymeric constituent b with other optional components) in.Binder component a) and the additive of optional other can be added in the following manner: for example before or after molded, or, carry out or do not carry out the evaporation of solvent or suspension/dispersion agent subsequently by dissolved or dispersive additive or additive agent mixture are applied in the polymer materials.They for example can be used as dry mixture or powder or are introduced directly into (for example, forcing machine, internal mixer or the like) in the processing units as solution or dispersion or suspension or melts.

To polymeric substrate b) in add binder component and can in all common hybrid machines, carry out, polymkeric substance is melted and mixes with additive in this mixing tank.Suitable machine is known for a person skilled in the art.They mainly are mixing tank, kneading machine and forcing machine.

Described method is preferably undertaken by add additive during processing in forcing machine.

Particularly preferred processing machine is single screw extrusion machine, reverse rotation and co-rotating twin screw extruder, planetary gear extruder, ring type forcing machine (ring extruders) or is total to kneader (cokneaders).Can also use and be equipped with the processing machine that at least one can use the degas chamber of vacuum to it.

Suitable forcing machine and kneading machine are described in, Handbuch der Kunststoffex-trusion for example, Vol.1Grundlagen, editor F.Hensen, W.Knappe, H.Potente, 1989, pp.3-7, ISBN:3-446-14339-4 (Vol.2 Extrusionsanlagen 1986, ISBN3-446-14329-7) in.

For example, spiro rod length is a 1-60 times of screw diameter, preferably 35-48 times of screw diameter.The speed of rotation of screw rod is 10-600 rev/min of (rpm), preferably 25-300rpm preferably.

Maximum throughput depends on screw diameter, speed of rotation and impellent.The weighing apparatus that dosage (dosage amounts) is sent in parameter that method of the present invention can also be mentioned by change or use carries out in the level that is lower than maximum throughput.

If the adding various ingredients, they can be by pre-mixings or add respectively.

Can also with binder component a) and the additive injection of optional other at polymeric substrate b) on.Additive agent mixture dilutes other additives (for example, above-mentioned conventional additives) or their melts, and they can also be ejected on the polymeric substrate with these additives like this.It is particularly advantageous adding by injection during the deactivation polymerizing catalyst; The steam of emitting in this case, (steam) can be used to deactivation catalyst.Under the polyolefine situation of pearl polymerization, may be favourable for example by spray application additive of the present invention (randomly with other additives).

Can also with the form of masterbatch (" enriched material ") with binder component a) and the additive of optional other join in the polymkeric substance, this masterbatch comprises concentration and is for example about 40.0 weight % of about 1.0 weight %-, and preferably the about 20.0 weight %'s of 2.0 weight %-is added into component in the polymkeric substance.This polymkeric substance be not must have the polymer phase that is added at last with additive wherein with structure.In aforesaid operations, polymkeric substance can use with the form of powder, particle, solution and suspension or with the form of lattices.

Can add before the shaping operation or during shaping operation.The material as herein described that comprises additive of the present invention is preferably used for producing moulded product, for example spinning block goods, injection mould goods, section bar (profiles) or the like and be fiber, melt-spun non-woven fabrics (spun meltnon-woven), film or foams especially.

Therefore, the invention further relates to molded or extruded product, fiber, melt-spun non-woven fabrics or the foams that comprise the present composition.

Following examples illustrate the present invention:

Embodiment

Material and method

PC 145 Resin (GE Plastics) at 120 ℃ by vacuum-drying 8 hours with use

P-EPQ (Ciba Specialty Chemicals) stablizes.DyneonPA5931 (=PTFE) be used as anti-dripping agent.

The polycarbonate compositions that is displayed in Table 1 is extruded on Haake TW-100 and carries out granulation by material bar granulation at 280 ℃.After 12 hours, according to Under-writer ' s Laboratories flame-retardancy standards UL-94, the composition of granulation is at 290 ℃ of plates that are injection molded to 1.6mm or 3.2mm thickness 120 ℃ of dryings.

Test flame retardant resistance according to UL-94 with vertical last formula.

Embodiment	The PC145 resin	IRGAFOS	FR	PTFE	UL-94
Embodiment	The PC145 resin	IRGAFOS	FR	PTFE	UL-94	1	99.32	0.08	0.1(1)	0.5	V-0(1.6mm)
2	99.32	0.08	0.1(2)	0.5	V-0(1.6mm)	1	99.32	0.08	0.1(1)	0.5	V-0(1.6mm)
2	99.32	0.08	0.1(2)	0.5	V-0(1.6mm)	3	99.32	0.08	0.1(3)	0.5	V-0(1.6mm)
4	99.82	0.08	0.1(1)	--	V-0(3.2mm)	3	99.32	0.08	0.1(3)	0.5	V-0(1.6mm)
4	99.82	0.08	0.1(1)	--	V-0(3.2mm)	5	99.57	0.08	0.1(4)	0.25	V-0(1.6mm)
6	99.32	0.08	0.1(4)	0.5	V-0(1.6mm)	5	99.57	0.08	0.1(4)	0.25	V-0(1.6mm)
6	99.32	0.08	0.1(4)	0.5	V-0(1.6mm)	7	99.57	0.08	0.1(5)	0.25	V-0(1.6mm)
The comparative example	99.92	0.08	-	--	V-2(1.6mm)	7	99.57	0.08	0.1(5)	0.25	V-0(1.6mm)

Be present in the fire retardant (FR) in the composition:

(1) TINOPAL SFP:4,4 '-two (2-amino-4-monoethanolamine amino-6-s-triazinyl)-two amido Stilbene-2,2 '-sodium disulfonate (structural formula in the above, referring to component definition a))

(2) TINOGARD HS:3-(2H-benzotriazole-2-yl)-4-hydroxyl-5-(1-methyl-propyl)-benzene sulfonic acid sodium salt (structural formula in the above, referring to component definition a))

(3) TINOPAL CBS:2,2 '-(4,4 '-biphenyl two bases two-2,1-ethene two bases)-DAADBSA disodium (structural formula in the above, referring to component definition a))

(4) TINOGARD AO 6 (structural formula in the above, referring to component definition a))

(5) TINOGARD AO 6 K (sylvite of TINOGARD AO 6 is referring to component definition a)).

Claims (according to the modification of the 19th of treaty)

1. composition, it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

Wherein

R ₁And R ₂Expression-NH independently of one another ₂,-NHC ₁-C ₄Alkyl ,-N (C ₁-C ₄Alkyl) ₂,-NH-hydroxyl-C ₂-C ₄Alkyl ,-N (hydroxyl-C ₂-C ₄Alkyl) ₂,-N (C ₁-C ₄Alkyl) (hydroxyl-C ₂-C ₄Alkyl), phenylamino, diphenylamino, by 1-3 be selected from-S (=O) ₂-O ^-M ⁺, C ₁-C ₄Alkyl and C ₁-C ₄Phenylamino or diphenylamino or 5-or 6 Yuans saturated N-heterocyclic radicals that the substituting group of alkoxyl group replaces;

R ₁' and R ₂' definition is as R ₁And R ₂With

Wherein

R ₁Expression hydrogen, C ₁-C ₄Alkyl or-S (=O) ₂-O ^-M ⁺Group;

R ₂Expression hydrogen or hydroxyl;

Wherein

R ₁And R ₂Represent hydrogen or substituting group independently of one another, this substituting group is selected from-S (=O) ₂-O-M ⁺, C ₁-C ₄Alkyl, phenyl-C ₁-C ₄Alkyl, hydroxyl and C ₁-C ₄Alkoxyl group;

Wherein

R ₁', R ₂' and R ₃', R ₁And R ₂Represent hydrogen or substituting group independently of one another, this substituting group is selected from-S (=O) ₂-O ^-M ⁺, C ₁-C ₄Alkyl, phenyl-C ₁-C ₄Alkyl, hydroxyl and C ₁-C ₄Alkoxyl group; With

a ₅) have an amphyl that the sulfo group of following formula replaces:

Wherein

R ₃Expression hydrogen or C ₁-C ₄Alkyl;

X represents C ₂-C ₆Alkylidene group;

Anti-dripping agent as annexing ingredient; With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

2. according to the composition of claim 1, it comprises tetrafluoroethylene as additional anti-dripping agent.

3. according to the composition of claim 1, it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

a ₁) triazinylaminostilbedisulphonic disulphonic acid salt (I), wherein

R ₁' and R ₂' definition is as R ₁And R ₂With

M ⁺The expression alkali metal atom;

a ₂) 2-(2-hydroxyphenyl)-2H-benzotriazole base sulfonate (II), wherein

R ₁Expression hydrogen;

R ₂Expression hydrogen; With

R ₃Expression hydrogen or C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom;

M ⁺The expression alkali metal atom; With

a ₅) amphyl (V) that replaces of sulfo group, wherein

R ₃Expression hydrogen or C ₁-C ₄Alkyl;

X represents C ₂-C ₆Alkylidene group;

M ⁺The expression alkali metal atom; With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

4. according to the composition of claim 1, it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from

a ₁) triazinylaminostilbedisulphonic disulphonic acid salt (I), wherein

R ₁And R ₂Expression-N (C independently of one another ₁-C ₄Alkyl) ₂, by 1 or 2-S (=O) ₂-O ^-M ⁺The phenylamino that replaces, or morpholinyl;

M ⁺The expression alkali metal atom; With

R ₁' and R ₂' definition is as R ₁And R ₂

a ₂) 2-(2-hydroxyphenyl)-2H-benzotriazole base sulfonate (II), wherein

R ₁Expression hydrogen or C ₁-C ₄Alkyl;

R ₂Expression hydrogen or hydroxyl; With

R ₃Expression hydrogen or C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom; With

a ₅) amphyl (V) that replaces of sulfo group, wherein

R ₃Expression hydrogen or methyl;

X represents C ₂-C ₄Alkylidene group;

M ⁺The expression alkali metal atom; With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

5. according to the composition of claim 1, it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

a ₁) triazinylaminostilbedisulphonic disulphonic acid salt (I), wherein

R ₁' and R ₂' definition is as R ₁And R ₂With

M ⁺The expression alkali metal atom;

a ₂) 2-(2-hydroxyphenyl)-2H-benzotriazole base sulfonate (II), wherein

R ₁And R ₂Expression hydrogen; With

R ₃Expression hydrogen or C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom; With

R ₁And R ₂Expression hydrogen;

M ⁺The expression alkali metal atom; With

a ₅) amphyl (V) that replaces of sulfo group, wherein

R ₁And R ₂The expression tertiary butyl;

R ₃Expression hydrogen;

X represents ethylidene;

Ar represents by the phenyl of 2 tertiary butyls replacements; With

M ⁺The expression alkali metal atom; With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

6. according to the composition of claim 1, it comprises

A) salt of at least a aromatic sulfonic acid, it is selected from:

With

With

a ₅) have amphyl that the sulfo group of following formula replaces salt:

With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

7. according to the composition of claim 1, it comprises other additives that are selected from polymer stabilizer and extra fire retardant in addition.

8. composition, it comprises:

a ₅) have an amphyl that the sulfo group of following formula replaces:

Wherein

R ₃Expression hydrogen or C ₁-C ₄Alkyl;

X represents C ₂-C ₆Alkylidene group;

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

9. the method for flame retardant resistance is provided to the polymeric substrate that comprises polycarbonate or polycarbonate Alloys, and this method comprises the salt that adds the aromatic sulfonic acid of claim 1 in described polymeric substrate.

Claims

1. composition, it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

Wherein

R ₁' and R ₂' definition is as R ₁And R ₂With

Wherein

R ₁Expression hydrogen, C ₁-C ₄Alkyl or-S (=O) ₂-O ^-M ⁺Group;

R ₂Expression hydrogen or hydroxyl;

Wherein

Wherein

a ₅) have an amphyl that the sulfo group of following formula replaces:

Wherein

R ₃Expression hydrogen or C ₁-C ₄Alkyl;

X represents C ₂-C ₆Alkylidene group;

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

2. according to the composition of claim 1, it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

a ₁) triazinylaminostilbedisulphonic disulphonic acid salt (I), wherein

R ₁' and R ₂' definition is as R ₁And R ₂With

M ⁺The expression alkali metal atom;

a ₂) 2-(2-hydroxyphenyl)-2H-benzotriazole base sulfonate (II), wherein

R ₁Expression hydrogen;

R ₂Expression hydrogen;

R ₃Expression hydrogen or C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom;

M ⁺The expression alkali metal atom; With

a ₅) amphyl (V) that replaces of sulfo group, wherein

R ₃Expression hydrogen or C ₁-C ₄Alkyl;

X represents C ₂-C ₆Alkylidene group;

M ⁺The expression alkali metal atom; With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

3. according to the composition of claim 1, it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from

a ₁) triazinylaminostilbedisulphonic disulphonic acid salt (I), wherein

R ₁' and R ₂' definition is as R ₁And R ₂With

M ⁺The expression alkali metal atom;

a ₂) 2-(2-hydroxyphenyl)-2H-benzotriazole base sulfonate (II), wherein

R ₁Expression hydrogen or C ₁-C ₄Alkyl;

R ₂Expression hydrogen or hydroxyl; With

R ₃Expression hydrogen or C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom; With

a ₅) amphyl (V) that replaces of sulfo group, wherein

R ₃Expression hydrogen or methyl;

X represents C ₂-C ₄Alkylidene group;

Ar represents by 1 methyl and 1 tertiary butyl or 2 phenyl that the tertiary butyl replaces; With

M ⁺The expression alkali metal atom; With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

4. according to the composition of claim 1, it comprises:

A) salt of at least a aromatic sulfonic acid, it is selected from:

a ₁) triazinylaminostilbedisulphonic disulphonic acid salt (I), wherein

R ₁' and R ₂' definition is as R ₁And R ₂With

M ⁺The expression alkali metal atom;

a ₂) 2-(2-hydroxyphenyl)-2H-benzotriazole base sulfonate (II), wherein

R ₁And R ₂Expression hydrogen; With

R ₃Expression hydrogen or C ₁-C ₄Alkyl; With

M ⁺The expression alkali metal atom; With

R ₁And R ₂Expression hydrogen;

M ⁺The expression alkali metal atom; With

a ₅) amphyl (V) that replaces of sulfo group, wherein

R ₁And R ₂The expression tertiary butyl;

R ₃Expression hydrogen;

X represents ethylidene;

Ar represents by the phenyl of 2 tertiary butyls replacements; With

M ⁺The expression alkali metal atom; With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

5. according to the composition of claim 1, it comprises

A) salt of at least a aromatic sulfonic acid, it is selected from:

With

With

a ₅) have an amphyl that the sulfo group of following formula replaces:

With

B) polymeric substrate comprises polycarbonate or polycarbonate Alloys.

6. according to the composition of claim 1, it comprises anti-dripping agent in addition as annexing ingredient.

8. the method for flame retardant resistance is provided to the polymeric substrate that comprises polycarbonate or polycarbonate Alloys, and this method comprises the salt that adds the aromatic sulfonic acid of claim 1 in described polymeric substrate.